Bis-phenol sulfate esters

ABSTRACT

A method for the production of compounds having the formula

United States Patent 1 1 1111 3,895,045

Firth, Jr. July 15, 1975 [54] BIS- PHENOL SULFATE ESTERS 3,401,148 9/1968 Schlott et a] 260/49 3,658,757 4 1972 C t I. 260 49 [751 Invent William Charles Wllmm 3,733,304 541973 26049 Conn. OTHER PUBLICATIONS [73] Asslgnee' Amencan Cyanamld Company Gilbert, Sulfonation and Related Reactions," p. 374,

Stamford, Conn. (1965) [22] Filed: Feb. 15, 1973 Primary Examiner-Howard T. Mars [21] Appl' 332381 Assistant Examiner-Norman Morgenstern Related US. Application Data Attorney, Agent, or Firm-Frank M Van Riet [62] Division of Ser. No. 153,862, June 16, 1971,

abandoned. [5 7] ABSTRACT A method for the production of compounds having 52 11.5. C1 260/457; 260/47 c; 260/47 ET; the f l 'M2- 1- 11' *yflH 1 1,;"369543 R1 51 lm. c1. g07c 141/14 SOs-A6030 [53] Field f Search 2 0 457 49 47 C, 47 ET wherein A is an aromatic radical, dihydroxy aromatic sulfate esters produced from said compounds, meth- [56] References Cited ods for the production of said esters and polymers UNITED STATES PATENTS produced therefrom, are disclosed. 3,236,808 2/ 1966 Goldberg et al. 260/49 6 Claims, N0 Drawings BIS-PHENOL SULFATE ESTERS CROSS-REFERENCE TO RELATED APPLICATIONS This application is a divisional of my abandoned application Ser. No. 153,862 filed June 16, 1971, entitled SYNTHESIS OF MONOMERS AND POLYMERS.

BACKGROUND OF THE INVENTION No. 3,401,148 is directed to the production of sulfurcontaining polyesters by reacting a diphenol with a diacid chloride in an inert organic solvent and in the presence of an aliphatic tertiary amine.

SUMMARY 1 have now discovered a unique class of dihydroxy aromatic sulfate esters which are useful for a multiplicity of applications. The esters are useful as intermediates in the production of polymers, themselves useful in film forming, as molded objects, as fibers and the like. The sulfate esters also find utility as additives by blending them via known procedures with other materials such as vinyl polymers, alkyd resins, aminoplast resins and the like.

DESCRIPTION OF THE INVENTION INCLUDING PREFERRED EMBODIMENTS The novel method of production of the abovementioned bischlorosulfates comprises reacting an aromatic dihydroxy compound with sulfuryl chloride according to the equation wherein A is an aromatic radical.

The reaction may be conducted at a temperature of from about C. to about 80C., preferably about -C. to about 65C. The temperature of the reaction is unexpectedly critical in determining the extent of chlorination in a side reaction. For example, the reaction of sulfuryl chloride with 2,2-bis(4-hydroxyphenyl)propane at 5C. to *C. leads to a low yield of the bischlorosulfate still containing excess chlorine after three recrystallizations. At a reaction temperature of 64 the bischlorosulfate was obtained in good yield with the theoretical chlorine content after one recrystallization. Reaction temperatures higher than -64 and an excess of sulfuryl chloride to compensate for that consumed by chlorination can be used to prepare high yields of chlorinated bischlorosulfates, as shown in Example 3. Usually a 2:1 molar ratio of sulfuryl chloride to the dihydroxyaromatic compound or a slight excess of the chloride is used. Atmospheric pressure is preferably employed, but subatmospheric or superatmospheric pressure may be used if necessary or desired.

The reaction is preferably conducted in the presence of a solvent which acts as an acid acceptor with such materials as tertiary amines, i.e. pyridine, triethyl amine, methyl pyridine and the like being exemplary and an inert solvent such as methylene chloride, ethyl ether, or ethyl acetate to moderate the exothermic reaction.

Although a solvent is not necessary in the production of the bischlorosulfates, such solvents as ethyl ether. ethyl acetate, methylene chloride and the like may be utilized.

Examples of materials which may be reacted with sulfuryl chloride according to the above equation include 2,2-bis-(4-hydroxypheny1)-propane (Bisphenol-A); bis-(2-hydroxyphenyl)-methane; bis-(4-hydroxyphenyl)- methane; l,l-bis-(4-hydroxyphenyl)-ethane; l,2-bis- (4-hydroxyphenyl)-ethane; 1,1-bis-(2-chloro-4- hydroxyphenyl)-ethane; l, 1 -bis-( 2,5 -dimethyl-4- hydroxyphenyl)-ethane; 2,2-bis-(4-hydroxynaphthyl)- propane; 2,2-bis-(4-hydroxyphenyl)-pentane; 2,2-bis- (4-hydroxyphenyl)-hexane; bis-(4-hydroxypheny1)- phenylmethane; bis-(4-hydroxyphenyl)- cyclohexylmethane; l,2-bis-(4-hydroxyphenyl)-1,2- bis-( phenyl )-ethane; 2,2-bis-(4-hydroxyphenyl)-1 phenylpropane; bis-(4-hydroxy-S-nitrophenyl methane; bis-(4-hydroxy-2,6-dimethyl-3- methoxyphenyl)-methane; 2,2-bis-(2,6-dichloro-4- hydroxyphenyl)-propane; 2,2-bis-(2-bromo-4-hydroxyphenyl)-propane, tetrabromobisphenol A and the like.

The preparation of these and other applicable compounds is known in the art. They are most commonly prepared by condensation of two moles of a phenol with a single mole of a ketone or aldehyde under known reaction conditions.

Also useful as charge materials in my novel process are the dihydroxybenzenes typified by hydroquinone and resorcinol; the dihydroxybiphenyls such as 4,4- dihydroxybiphenyl; 2,2-dihydroxybiphenyl; 2,4- dihydroxybiphenyl and the dihydroxynaphthalenes such as 2,6-dihydroxynaphthalene, etc.

Dihydroxyaryl sulfones are also useful as charge materials. Sulfones such as bis-(4-hydroxyphenyl)- sulfone; 2,4-dihydroxyphenyl sulfone; 2,4'-dihydroxy- 5 '-chlorophenyl sulfone; 3 '-chloro-4,4 dihydroxyphenyl sulfone; bis-(4-hydroxyphenyl)- biphenyl disulfone, etc. being exemplary. The preparation of these and other useful dihydroxyarylsulfones is described in U.S. Pat. No. 2,288,282 to I-luissmann. Polysulfones, as well as sulfones substituted with halogen, nitro, alkyl and other substituents are also useful. In addition, related sulfides and sulfoxides are applicable.

Dihydroxyaromatic ethers are also useful and may be prepared by methods found in Pat. No. 2,739,171 to Linn, and in Chemical Reviews, 38, 414-417 (1946). Typical of such dihydroxyaryl ethers which may be reacted with sulfuryl chloride according to my novel method are the following: 4,4-dihydroxypheny1 ether; 4,4-dihydroxy-2,6-dimethylphenyl ether; 4,4-

dihydroxy-3,3'-diisobutylpheny1 ether; 4,4'-dihydroxy- 3,3-diisopropylphenyl ether; 4,4'-dihydroxy-3,2'- dinitrophenyl ether; 4,4 '-dihydroxy-3 ,3 dichlorophenyl ether; 4,4'-dihydroxynaphthyl ether; 4,4'-dihydroxy-2,6-dimethoxyphenyl ether and the like. The many other types of suitable dihydroxyaryl compounds will be apparent to those skilled in the art.

The bischlorosulfate monomers produced according to my novel process are generally white solids which melt without decomposition. They appear to be more stable to moisture than most other acid chlorides.

The bischlorosulfate of 2,2-bis-(4-hydroxyphenyl)- propane has two solid modifications, which have slightly different melting points and infrared spectra. One modification (A in Table I) has a melting point of 79.5 82.5 and a distinctive infrared band at 821 cm. The other modification (B) has a melting point of 725 75.0 and a characteristic infrared band at 803 cm. Both modifications gave the same theoretical analysis for carbon, hydrogen, sulfur and chlorine. Mixtures of the two modifications can be prepared. Polymorphism of this type is, of course, known in a great many organic compounds (R. S. Tipson, in Tee/1- nique of Organic Chemistry, A. Weissberger, Ed., Interscience Publishers lnc., New York, N.Y., 1950, pp. 391-393).

The novel aromatic sulfate esters of the instant invention have the formula wherein A in each instance is the same or a different aromatic radical and m is an integer of 1-2, inclusive. Because of a side reaction, discussed in more detail below, the sulfate esters contain 1-5 percent chlorine.

The sulfate esters of Formula 1 are produced according to the equation (A) wherein A and m are as defined above.

The products are amber, low-melting brittle solids. Elemental analysis shows the presence of chlorine, while infrared spectroscopy and nuclear magnetic resonance spectroscopy show the presence of hydroxyl groups.

The reaction is carried out via Equation A, generally with a molar ratio of phenol to chloride of 1:1 to 2:1, respectively. The use of the 2:1 ratio gives esters containing lesschlorine and less sulfate than the 1:1 ratio. If desired even more of the phenol can be used.

Reactions of aromatic bischlorosulfates with dihydroxyaromatic compounds in a 1:1 molar ratio were initially intended to produce aromatic polysulfates, such as those described in my copending application, Ser. No. 130,528, filed Apr. 1, 1971, entitled SYN- THESIS OF MONOMERS AND POLYMERS now US. Pat. No. 3,733,304. Because of the surprising side reactions which result in chlorination and the genera tion of hydroxyl groups, the products contain at most only about two sulfate groups. (This is, of course, the average composition of the mixture of compounds in the product.) The chlorination is believed to take place on the aromatic rings, but this concept is not to be construed as a limitation of the instant invention.

The reactions are allowed to proceed for about 2-7 hours, i.e. until essentially complete conversion is achieved, although longer or shorter reaction times may be used.

Temperatures ranging from about 25C. to abo: 150C. may be used, preferably 75125C. Atmo spheric pressure is preferred, but subatmospheric superatmospheric pressure can be used.

The reactions are conducted in the presence of an acid acceptor such as pyridine.

The aromatic sulfate esters (1) contain hydroxyl end groups which permit them to be extended with difunctional compounds such as bischloroformates, diisocyanates, dibasic acids or-esters', etc. toproduce mixed poly(sulfate/carbonates), -poly(sulfate/urethanes), poly(sulfate/esters) and the like.

For example, utilizing phosgene as the carbonate forming reactant, high molecular weight poly(sulfate/- carbonates) are produced according to the equation wherein A and m are as indicated above and x represents the number of recurring units in the polymer.

In order to obtain high molecular weights in these extension reactions, small amounts of unchanged chlorosulfate groups must sometimes be removed by a preliminary hydrolysis step. This step is not always necessary, but depends on the time and temperature used in the preparation of the dihydroxyaromatic sulfate esters and the molecular weight sought in the extension reaction.

The poly(sulfate/carbonates) are a versatile and useful class of polymers. The combination of high softening temperature, desirable strength characteristics and thermal and chemical stability make these compositions useful as thermoplastic molding compounds for the fabrication of molded gaskets, tubing, gears etc. either alone or combined with such fillers as silica, carbon black, wood flour etc. Films thereof are useful as packaging material, containers, covers, liners, insulation, recording tapes, photographic film base, pipe wrappings etc. They may be oriented or drawn at suitable temperatures to permit enhancement of strength properties such as tensile and flexural strengths and may be amorphous or crystalline. Fibers may also be readily formed by melt or solution spinning and are useful as yarn, thread, bristle, rope and the like. The polymers of this invention may be readily pigmented or dyed, suitable stabilizers and plasticizers as are known in the art may be incorporated therein and alloying with other resinous materials may be accomplished. The present compositions may also be used as surface coatings in paints, varnishes and enamels and their powerful adhesive qualities render them particularly useful as adhesives for plastic, rubber, metal, glass or wood parts.

The following examples are set forth for purposes of illustration only and are not to be construed as limitations on the present invention except as set forth in the appended claims. All parts and percentages are by weight unless otherwise specified.

EXAMPLE 1 to 0?. Asoluti on of 200 parts of water and 24 parts of concentrate dhydrochloric acid is then added. The resultant methylene chloride layer is extracted twice with aqueous hydrochloric acid, thrice with water and dried in two stages with anhydrous sodium sulfate. The meth- Z M 3 ylene chloride isremoved under vacuum to give 207 parts of white solid bischlorosulfate,

is recovered.

v EXAMPLE 9 (ll-S0 c $0 -01,

l I 2,2-Bis(3,5-dibrom0-4-hydroxyphenyl)-propane CH} 10 (54.4 parts), pyridine (16 parts) and sulfuryl chloride (27 parts) are combined as in Example 1. The product is isolated in the usual wa After t 11' 't' m.p. 70.5 74.5C., 17.4% C1, 803 cm absorption. white Solid y recrys a I [on The product is recrystallized from hexane at 25 with exclusion of moisture to give 178 parts of isopropylidene-di-p-phenylene chlorosulfate; m.p. 15 CH Br 72.5-75.0c. 3

Anal. Calcd. for C H CI O S C, 42.36; H, 3.32; 01.50 g SO3 C1 C1, 16.67; S, 15.08. Found: C, 42.41; H, 3.40; CI, I 16.76; S, 15.03. CH

The infrared spectrum shows a weak peak at 803 Br cm which is characteristic of the solid modification B.

15 obtained. EXAMPLES 2-5 EXAMPLE 10 Following the procedure of Example 1, various runs are conducted varying the reaction temperature and the molar ratio of reactants. In these runs the methylene chloride layer is extracted several times with a mixture of dilute sodium hydroxide solution and ice just before being dried with anhydrous sodium sulfate. The

Hydroquinone (22.0 parts), pyridine (32 parts) and sulfuryl chloride (54 parts) are allowed to react in methylene chloride solution as in Example 1. Recrystallization of the isolated product gives results are set forth in Table 1, below. In Example 5 the Cl SO infrared spectrum showed a weak peak at 821 cm, 3 S03 G1 which is characteristic of solid modification A.

Found: C, 42.31; H, 3.32; Cl, 16.82; S, 15.11 in good yield.

TABLE I Preparation of the Bischlorosulfate of 2,2-Bis(4-hydroxyphenyl)propane Purified Bischlorosulfate Bis- Sulfuryl Pyri- Crude Solid phenol A Chloride dine Reaction Product No. of Yield Modifi- EX. parts parts parts Temp., 20C. parts Cl" recryst." parts mp Cl cation 1 1 14.2 143 87 64 207.4 17.44 1 178 72.5-75 16.76 B 2 45.6 54.4 32 5 to 10 46.9 3 12.5 74-78.5 17.49 A 3 91.2 162.4 97 -24 to 28" 166.4 1 131 65.5-68.5 18.77 B 2 107 67.5-70.5 18.17 B 4 91.2 119 97 155 17.3 1 120 67.5-71.5 17.89 B 5 114.2 135.0 79 64 140 16.85 1 111 79.5-82.5 16.82 A

"The theoretical chlorine content of the crude bischlorosulfate is 16.67%. "Recrystullized from n-hexane at 1 3 to 25.

EXAMPLE 6 EXAMPLE 11 The procedure of Example 1 is again followed except 44, Dihydr0xydiphenyl sulfone (95% isomer that ethyl ether is substituted for the methylene chlo- 250 parts), pyridine (16 parts) and sulfuryl chloride ride solvent thereof. Similar results are achieved. (27 parts) are allowed to react in methylene Chloride solution as in Example 1. After isolation the crude product is recrystallized and EXAMPLE 7 The use of ethyl acetate as a solvent for the methylene chloride of Example 1, all else remaining equal, gives similar results.

EXAMPLE 8 c1 so p,p'-Biphenol (18.6 parts), pyridine (16 parts) and sulfuryl chloride (27' parts) are allowed to react in methylene chloride solution as in Example 1. The product is recrystallized and an excellent yield of white solid, 1 is recovered.

O: CQIO 7 EXAMPLES 12-18 (Production of Esters) These reactions are carried out under nitrogen and 8 The product is added to vigorously stirred water to precipitate the polymer. The polymer is isolated, washed with water', sti'rred for '10 minutes with hot water (ca. 80), collecte'd 'byfilt'ration, washed with water. and dried underv'acuumat 80C. The polymer is with the exclusion of molsture- The experlmemal reprecipitated from methylene chloride solution with tails are summarized in Table 11. The products are dish l d d i d nd vacuum t 80, El l solved in methylene chloride and extracted With COld analyses and viscgsitiegof the polymers are shown in dilute hydrochloric acid and then with water until the Table 111. The polymer of Example 19 is derived from aqueous layer is neutral. The methylene chloride solu- 10 the ester of Example 12 etc. tions are dried with sodium sulfate, and the products Physical properties of compression-molded samples isolated by removal of the methylene chloride under of the polysulfate polycarbonate from Example 25 are vacuum. given in Table IV. 1

TABLE 11 Bisphenol A Bischlorosulfate Pyridine Conditions Product Example parts parts C parts hr "C. parts 1:1 REACT ANT MOLE RATIO 12 1.07 1.99 17.22 1.5 4 120 1.9 13 2.24 4.17 17.49 3.2 2" 120 4.7 14 2.09 3.89 16.76 2.9 2 100 4.6

2:1 REACT ANT MOLE RATIO l5 2.19 2.04 17.22 1.5 2 100 3.0 16 3.26 3.03 17.49 2.3 2** 120 4.8 17 3.06 2.8 17.49 2.2, 2 80 4.5 18 171.7 160.0 18.16 119 2' 100 289 "Theoretical chlorine content: 16.677: "Used shaking Used stirring 4 hours at 80C.; 1 hour at 100C; 2 hours at 120C. "2 hours at 80C.; 1 hour at 100C; 2 hours at 120C.

- TABLE 111 NaOH Derived polysulfate polycarbonate Example Treatment C H S Cl SO :CO ClzS ninh 19 No 62.77 4.71 7.38 4.87 1.9 0.60 0.20 20 Yes 62.50 4.63 7.20 4.86 1.9 0.61 0.26 21 Yes 64.94 4.76 6.18 4.20 1.3 0.61 0.40 22 No 66.80 5.05 6.74 1.50 1.4 0.20 0.28 23 No 66.23 5.11 6.62 1.66 1.4 0.23 0.50 24 Yes 67.24 5.27 5.92 1.38 1.1 0.21 0.64 25 Yes 65.90 5.08" 6.30 2.46 1:31 0.35 0.54

"Determined on benzene solutions at 0.5% concentration EXAMPLES 19-25 TABLE [V Some of the crude products of Examples 12-18 are treated with aqueous sodium hydroxide to hydrolyze small amounts of unchanged chlorosulfate groups, which otherwise would limit the molecular weight of the polysulfate polycarbonate.

Typically the crude product is heated at reflux for one hour with 0.5 N sodium hydroxide solution (30 parts/part). The product is acidified with cold, dilute hydrochloric acid (10 parts concentrated hydrochloric acidparts waterl00 parts ice per parts of sodium hydroxide solution) and extracted with methyl- 0 ene chloride. The methylene chloride solution is ex-- tracted with water until the extracts are neutral r" E then dried with sodium sulfate. The product is re: ered by removing the methylene chloride under 1 uum.

The esters are dissolved in reagent grade pyridii and stirred vigorously while phosgene is slowly bubbled in. The end point is indicated by a viscosity increase.

Properties of Molded Poly(sulfate/carb0nate) (of Example 25) Transparency transparent X-ray pattern amorphous Flexural strength. psi 17,500 Flexural modulus, psi 404,000 Tensile strength, psi 9,800

lzod impact strength 0.6

(ft. 1b./in. notch,

Ma bar) Rockwell Hardness, M" scale 72 Glass transition temperature 107C.

(by differential thermal analysis) 9 10 chlorosulfate of Bisphenol A and other conditions y f y y i therefor, are disclosed in Table V. 26. 4.4'-dihydroxy-3.2-dinitrophe y h Properties of the sulfate/carbonate polymers are 4.4'-dihydroxy-3.3'-dichlorophenyl eth and shown in Table VI. 28. 4,4'-dihydroxy-2,o-dimethoxyphenyl ether 5 TABLE V Bischlorosulfate of Pyridine Product Example Dihydroxy Compound, parts Bisphenol A", parts pans parts 26 p,p'-biphenol l .79 4.08 3.0 4.0 27 4,4'-oxydiphenol 1.85 3.89 2.9 3.2

"The hischlorosulfale contained l6.76% chlorine; theoretical chlorine content: 16.67%.

TABLE VI and m is a whole, positive integer of 1,2, inclusive.

2. An ester according to claim 1 wherein A is Properties of Poly(sulfate/carbonates) of Examples 26 and 27 De' d l lft/ t HVC p0 Su 3 ecar 0113 e I I q Example 26' "Ari! W308 %Cl l ci= R "inh"' C 26 61.53 3.95 7.78 4.66 0.54 0.37 I 27 59.92 4.32 7.74 4.] l 0.48 0.]9 CH 3 "Determined in methylene chloride at 30C.. 0.57: concentration. 3, AI] ester according to claim 1 wherein A is I claim: 1. A dihydroxyaromatic sulfate ester having the for- 4, An e ter according to claim 1 wherein one A is mula HO-A -(-OSO O-A )-,,,OH CH wherein A in each instance is the same or a different g and is a radical defined by abstraction of the hydroxy I groups from a compound selected from the group con- CH sisting of 3 l. 2,2-bis-(4-hydroxyphenyl)-propane; d h other A i 2. bis-(Z-hydroxyphenyl)-methane; 3. bis-(4-hydroxyphenyl)-methane; 4. l,l-bis-(4-hydroxyphenyl)-ethane; 5. l,2-bis-(4-hydroxyphenyl)-ethane; v y yp i 5. An ester according to claim 1 wherein one A is 7. l, 1 -bis-( 2,5-dimethyl4-dihydroxyphenyl)-ethane; 8. 2,2-bis-(4-hydr0xynaphthyl)-propane; 9. 2,2-bis-(4-hydroxyphenyl)-pentane; A l0. 2,2-bis-(4-hydroxyphenyl)-hexane; l l. bis-(4-hydroxyphenyl)phenylmethane; and the other A is 12. bis-(4-hyclroxyphenyl)-cyclohexylmethane; l3. l,2-bis-(4-hydroxyphenyl)-1,2-bis-(phenyl)- CH ethane; I I4. 2,2-bis-(4-hydroxyphenyl)-l-phenylpropane; C 15. bis-(4-hydroxy-5-nitr0phenyl)-methane;

i 6. bis-( 4-hydroxy-2,6-dimethyl-3-methoxyphenyl)- H 3 methane; 2,2'b1 $'(2i6dlchlom'4'hydroxyphenyl)'prpane; 6. An ester according to claim 1 wherein A is 18. 2,2-b1s-(2-br0mo-4hydroxyphenyl)-pr0pane; l9. tetrabrornobisphe-nol- Aw?- y O 20. dihydroxybenzenes; 21. dihydroxybiphenyls; 5 22. dihydroxynaphthalenes; H 23. dihydroxyaryl sulfones; O

24. dihydroxyaryl sulfones further substituted with halogen or nitro groups; 

1.A DIHYDROXYAROMATIC SULFATE ESTER HAVING THE FORMULA
 2. An ester according to claim 1 wherein A is
 2. BIS-(2-HYDROXYPHENYL)-METHANE,
 2. bis-(2-hydroxyphenyl)-methane;
 3. bis-(4-hydroxyphenyl)-methane;
 3. BIS-(4-HYDROXYPHENYL)-METHANE,
 4. 1,1-BIS-(4-HYDROXYPHENYL)-ETHANE,
 5. 1,2-BIS-(4-HYDROXYPHNYL)-ETHANE,
 6. 1,1-BIS-(2-CHLORO-4-HYDROXYPHENYL)-ETHANE,
 7. 1,1-BIS-(2,5-DIMETHYL-4-DIHYDROXYPHENYL)-ETHANE,
 8. 2,2-BIS-(4-HYDROXYNAPHTHYL)-PROPANE,
 9. 2,2-BIS-(4-HYDROXYPHENYL)-PENTANE, 10 2,2-BIS-(4-HYDROXYPHENYL)-HEXANE,
 3. An ester according to claim 1 wherein A is
 4. An ester according to claim 1 wherein one A is
 4. 1,1-bis-(4-hydroxyphenyl)-ethane;
 5. 1,2-bis-(4-hydroxyphenyl)-ethane;
 5. An ester according to claim 1 wherein one A is
 6. An ester according to claim 1 wherein A is
 6. 1,1-bis-(2-chloro-4-hydroxyphenyl)-ethane;
 7. 1,1-bis-(2,5-dimethyl-4-dihydroxyphenyl)-ethane;
 8. 2,2-bis-(4-hydroxynaphthyl)-propane;
 9. 2,2-bis-(4-hydroxyphenyl)-pentane;
 10. 2,2-bis-(4-hydroxyphenyl)-hexane;
 11. bis-(4-hydroxyphenyl)-phenylmethane;
 11. BIS-(4-HYDROXYPHENYL)-PHENYLMETHANE,
 12. BIS-(4-HYDROXYPHENYL)-CYCLOHEXYLMETHANE,
 13. 1,2-BIS-(4-HYDROXYPHENYL)-1,2-BIS-(PHENYL)-ETHANE,
 14. 2,2-BIS-(HYDROXYPHENYL)-1-PHENYLPROPANE,
 12. bis-(4-hydroxyphenyl)-cyclohexylmethane;
 13. 1,2-bis-(4-hydroxyphenyl)-1,2-bis-(phenyl)-ethane;
 14. 2,2-bis-(4-hydroxyphenyl)-1-phenylpropane;
 15. bis-(4-hydroxy-5-nitrophenyl)-methane;
 15. BIS-(4-HYDROXY-5-NITROPHENYL)-METHANE,
 16. BIS-(4-HYDROXY-2,6-DIMETHYL-3-METHOXYPHENYL)METHANE,
 17. 2,2-BIS-(2,6-DICHLORO-4-HYDROXYPHENYL)-PROPANE,
 18. 2,2-BIS-(2-BROMO-4-HYDROXYPHENYL)-PROPANE,
 16. bis-(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)-methane;
 17. 2,2-bis-(2,6-dichloro-4-hydroxyphenyl)-propane;
 18. 2,2-bis-(2-bromo-4-hydroxyphenyl)-propane;
 19. tetrabromobisphenol A;
 19. TETRABROMOBISPHENOL A,
 20. DIHYDROXYBENZENES,
 20. dihydroxybenzenes;
 21. dihydroxybiphenyls;
 21. DIHYDROXYBIPHENYLS,
 22. DIHYDROXYNAPHTHALENES,
 22. dihydroxynaphthalenes;
 23. dihydroxyaryl sulfones;
 23. DIHYDROXYARYL SULFONES,
 24. DIHYDROXYARYL SULFONES FURTHER SUBSTITUTED WITH HALOGEN OR NITRO GROUPS,
 24. dihydroxyaryl sulfones further substituted with halogen or nitro groups;
 25. dihydroxyaryl ethers;
 25. DIHYDROXYARYL ETHERS,
 26. 4,4''-DIHYDROXY-3,2''-DINITROPHENYL ETHER,
 27. 4,4''-DIHYDROXY-3,3''-DICHLOROPHENYL ETHER, AND
 28. 4,4''-DIHYDROXY-2,6-DIMETHOXYPHENYL ETHER AND M IS A WHOLE, POSITIVE INTEGER OF 1,2, INCLUSIVE.
 26. 4,4''-dihydroxy-3,2''-dinitrophenyl ether;
 27. 4,4''-dihydroxy-3,3''-dichlorophenyl ether; and
 28. 4,4''-dihydroxy-2,6-dimethoxyphenyl ether and m is a whole, positive integer of 1,2, inclusive. 